CN106189961A - A kind of footwear low temperature resistant EVA binding agent and preparation method thereof - Google Patents

A kind of footwear low temperature resistant EVA binding agent and preparation method thereof Download PDF

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Publication number
CN106189961A
CN106189961A CN201610598538.6A CN201610598538A CN106189961A CN 106189961 A CN106189961 A CN 106189961A CN 201610598538 A CN201610598538 A CN 201610598538A CN 106189961 A CN106189961 A CN 106189961A
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eva
weight portion
footwear
low temperature
temperature resistant
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CN201610598538.6A
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CN106189961B (en
Inventor
马爱芬
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Huizhou Sikai Shoes Co., Ltd.
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马爱芬
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/026—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-vinylester copolymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention provides a kind of footwear low temperature resistant EVA hot-melt adhesive and preparation method thereof, specifically comprise: EVA 100 weight portion, POE 25 40 parts, maleic anhydride 5 10 weight portion, bicyclo-defend diene series Petropols 10 15 weight portion, low molecular weight polyurethane 18 22 weight portion, paraffin 35 weight portion, cross-linking agent 4 10 weight portion, coupling agent 13 weight portion, antioxidant 25 weight portion, ultraviolet absorber 05 weight portion, Graphene 37 weight portion.Final products have good lower temperature resistance, pliability and cementability, can meet use long-term under cryogenic conditions.

Description

A kind of footwear low temperature resistant EVA binding agent and preparation method thereof
Technical field:
The present invention relates to a kind of footwear EVA adhesive field, be specifically related to one and there is footwear EVA low temperature resistant, flexible glue Mixture field.
Background technology:
EVA, owing to introducing VAM in strand, thus reduces high-crystallinity, improve toughness, impact resistance, Filler intermiscibility and heat seal performance, PUR is the field that one is important.EVA hot-melt adhesive is a kind of solvent-free, without moisture The polymer of solid meltability, be solid at normal temperatures, heating is molten to a certain degree become to flow and having certain viscosity Liquid adhesive, be light brown translucent body or this white after it is melted.
Shoe industry belongs to labor-intensive production, and China has a large population, market is big, labour force is sufficient and low cost, gives birth to every year Producing more than 100 hundred million pairs of footwear, every pair of footwear are substantially required for binding agent and carry out the bonding of part-structure, especially leather shoes and sneakers, mainly For exporting.The countries such as Russia are main outlet object, but Russia's weather is low, and part EVA bonding agent is the most difficult To use, under low temperature, reduction of pliability is quickly, it is difficult to meet the needs of low temp area, have impact on the export volume of specific region.
Summary of the invention:
Goal of the invention: in order to solve above-mentioned technical problem, it has good to the invention provides a kind of low temperature resistant EVA hot-melt adhesive of footwear Good lower temperature resistance, pliability and cementability, can meet use long-term under cryogenic conditions.Simultaneously.Present invention also offers A kind of footwear preparation method of low temperature resistant EVA hot-melt adhesive.
The technical scheme solving the problems referred to above is:
A kind of footwear are with low temperature resistant EVA binding agent, it is characterised in that: EVA 100 weight portion, ethylene-octene copolymer 25-40 part, Maleic anhydride 5-10 weight portion, bicyclo-defend diene series Petropols 10-15 weight portion, low molecular weight polyurethane 18-22 weight portion, Paraffin 3-5 weight portion, cross-linking agent 4-10 weight portion, coupling agent 1-3 weight portion, antioxidant 2-5 weight portion, ultraviolet absorber 0-5 Weight portion, Graphene 3-7 weight portion.
Described EVA is made up of two kinds of EVA, wherein an EVA be VA content in 25-27%, melt index 110-130, second EVA is VA content 20-22%, melt index 220-260.Present invention employs mixing EVA, different melt index affect PUR Mobility after fusing, general PUR needs certain mobility, meets dispersed on adherend surface of PUR；With Time, the bonding force of PUR can be regulated by VA content, and in order to balance mobility and bonding force, the present invention have selected specifically Melt index and VA content.Not in the combination of this scope, its mobility and bonding force are difficult to balance, are only capable of meeting a kind of one Individual performance.
As preferred technical scheme, the weight ratio of an EVA and the 2nd EVA is 5:2-5.
The present invention also uses ethylene-octene copolymer, its tough excellent effect, but it have impact on system to a certain extent Bonding force, therefore first EVA, ethylene-octene copolymer are mixed with maleic anhydride, maleic anhydride is to EVA, ethylene-octene Copolymer is modified, and substantially increases its cohesive by modification, not only meets cohesive but also improve the pliability of system.
The addition of low molecular weight polyurethane improves bond properties and the pliability of PUR, by later stage cross-linking reaction In, it is not involved in crosslinking, and it is as a flexible polymer, in the cross-linked structure of EVA, serves stress dispersion and makees With, the half interpenetrating network structure in similar " hydrogel " field, can effectively improve load bearing effect, and polyurethane has well Lower temperature resistance.
As optimal technical scheme, described low molecular weight polyurethane is low molecular polyether type polyurethane, and polyether-type is than poly- Ester type has more preferable pliability, and as more preferably technical scheme, low-molecular-weight is 500-2000, can make in this molecular weight It preferably moves in cross-linked structure, and the most within the range, its stress dispersion effect there will be substantially variation.
Described cross-linking agent is cumyl peroxide.
Graphene is employed herein, and Graphene is lamellar, excellent in mechanical performance, and stress can be made in addition system fast Speed dispersion, improves its weight capacity.As optimal technical scheme, should be greater than 10 μm at the full-size of described Graphene, greatly The Graphene of size is a big stress surface, and stress more can be disperseed in a wider context, and stress conduction velocity is faster.
Described coupling agent is the coupling agent containing acryloxy, and the use of coupling agent serves adhesion promoter, carries Active force between high different interfaces, meanwhile, uses the coupling agent of acryloxy, and acryloyl-oxy has higher polarity, Can improve the active force of itself and EVA, adhesion strength relatively uses other kinds of coupling agent to improve and becomes apparent from.
Prepare the footwear method with low temperature resistant EVA binding agent, it is characterised in that: comprise the steps:
(1) EVA, ethylene-octene copolymer are mixed with maleic anhydride, EVA and ethylene-octene copolymer are changed Property；
(2) remaining ingredient with maleic anhydride modified after EVA and ethylene-octene copolymer mix homogeneously, between 120-175 DEG C Carry out reacting 2 hours, obtain the low temperature resistant EVA binding agent of footwear.
Technique effect:
The present invention is passed through compounding balance mobility and the bonding force of EVA, is grafted by ethylene-octene copolymer and maleic anhydride Modification improves toughness and bonding force；Low molecular weight polyurethane forms semi-intercrossing network, the large stretch of Graphene of use can be effective Improve force dispersion effect；Coupling agent containing acryloxy improves bonding force.Product centering is all glued by above-mentioned each component Make a concerted effort, mobility, stress dispersibility, and the flexible component of the most many increases also improves stress under lower temperature resistance, low temperature Dispersibility.In order to balance various performance, each amounts of components of the present invention selects to also play vital effect.
Detailed description of the invention:
Principle and feature to the present invention are described below, and example is only intended to explain the present invention, is not intended to limit The scope of the present invention.
Embodiment 1:
The footwear preparation method of low temperature resistant EVA binding agent, key step includes the following:
(1) by VA content 26%, EVA 50 weight portion of melt index 120, VA content 22%, the second of melt index 240 EVA 50 weight portion, ethylene-octene copolymer 30 weight portion mix with maleic anhydride 10 weight portion, to EVA and ethylene-pungent Alkene copolymer is modified；
(2) dicyclopentadiene petroleum resin 10 weight portion, molecular weight be 1000 polyurethane 20 weight portion, paraffin 4 weight portion, friendship Connection agent cumyl peroxide 5 weight portion, coupling agent 2 weight portion, antioxidant 3 weight portion, ultraviolet absorber 4 weight portion, maximum At size 22 micron graphite alkene 4 weight portions with maleic anhydride modified after EVA and ethylene-octene copolymer mix homogeneously, Carry out between 120-175 DEG C reacting 2 hours, obtain the low temperature resistant EVA binding agent of footwear.
Other embodiments and comparative example see table:
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
Oneth EVA 50 50 62.5 50 50 100 0 65 50 50
2nd EVA 50 50 37.5 50 50 0 100 65 50 50
Ethylene-octene copolymer 30 30 30 30 30 30 30 0 30 30
Maleic anhydride 10 10 10 10 10 10 10 10 0 10
Dicyclopentadiene petroleum resin 10 10 10 10 10 10 10 10 10 0
C9 resin 0 0 0 0 0 0 0 0 0 10
The polyurethane of molecular weight 1000 20 0 20 20 20 20 20 20 20 20
The polyurethane of molecular weight 3000 0 20 0 0 0 0 0 0 0 0
Paraffin 4 4 4 4 4 4 4 4 4 4
Cumyl peroxide 5 5 5 5 5 5 5 5 5 5
Containing acryloxy coupling agent 2 2 2 2 0 2 2 2 2 2
KH550 0 0 0 0 2 0 0 0 0 0
Antioxidant 3 3 3 3 3 3 3 3 3 3
Ultraviolet absorber 3 3 3 3 3 3 3 3 3 3
22 μm Graphenes 5 5 5 0 5 5 5 5 5 5
5 μm Graphenes 0 0 0 5 0 0 0 0 0 0
T-shaped peel strength/KN/m (flexible PU is bonding) at 20 DEG C 6.2 5.8 5.6 6.1 5.6 4.6 6.2 4.9 4.5 5.7
T-shaped peel strength/KN/m (flexible PU is bonding) at-10 DEG C 6.0 5.6 5.2 5.9 5.1 4.1 5.9 4.3 4.0 5.4
T-shaped peel strength/KN/m (flexible PU is bonding) at-30 DEG C 5.6 5.3 5.0 5.4 4.8 3.6 5.7 4.1 4.5 5.0
Voltage-withstand test/time 300 circulations have no damaged 295 288 261 263 234 223 241 221 268
Voltage-withstand test for being solidified into the cylinder of diameter 1cm, highly 1cm by binding agent, after using stress test to be pressed downward against being reduced to 70% Release.

Claims (9)

1. footwear are with low temperature resistant EVA binding agent, it is characterised in that: EVA 100 weight portion, ethylene-octene copolymer 25-40 Part, maleic anhydride 5-10 weight portion, bicyclo-defend diene series Petropols 10-15 weight portion, low molecular weight polyurethane 18-22 weight Part, paraffin 3-5 weight portion, cross-linking agent 4-10 weight portion, coupling agent 1-3 weight portion, antioxidant 2-5 weight portion, ultraviolet absorber 0-5 weight portion, Graphene 3-7 weight portion.
2. footwear as claimed in claim 1 are with low temperature resistant EVA binding agent, it is characterised in that: described EVA is made up of two kinds of EVA, its In an EVA be VA content in 25-27%, melt index 110-130, the 2nd EVA is VA content 20-22%, melt index 220- 260。
3. footwear as claimed in claim 2 are with low temperature resistant EVA binding agent, it is characterised in that: an EVA and the weight of the 2nd EVA Ratio is 5:2-5.
4. footwear as claimed in claim 1 are with low temperature resistant EVA binding agent, it is characterised in that: first by EVA, ethylene-octene copolymerization Thing mixes with maleic anhydride, and EVA, ethylene-octene copolymer are modified by maleic anhydride.
5. footwear as claimed in claim 1 are with low temperature resistant EVA binding agent, it is characterised in that: described low molecular weight polyurethane is low Molecular weight polyisoprene ether-based polyurethane, low-molecular-weight is 500-2000.
6. footwear as claimed in claim 1 are with low temperature resistant EVA binding agent, it is characterised in that: described cross-linking agent is that peroxidating two is different Propyl benzene.
7. footwear as claimed in claim 1 are with low temperature resistant EVA binding agent, it is characterised in that: at the full-size of described Graphene Should be greater than 10 μm.
8. footwear as claimed in claim 1 are with low temperature resistant EVA binding agent, it is characterised in that: described coupling agent is containing acryloyl The coupling agent of epoxide.
9. preparation claim 1-8 arbitrary described footwear method of low temperature resistant EVA binding agent, it is characterised in that: include walking as follows Rapid:
(1) EVA, ethylene-octene copolymer are mixed with maleic anhydride, EVA and ethylene-octene copolymer are changed Property；
(2) remaining ingredient with maleic anhydride modified after EVA and ethylene-octene copolymer mix homogeneously, between 120-175 DEG C Carry out reacting 2 hours, obtain the low temperature resistant EVA binding agent of footwear.
CN201610598538.6A 2016-07-27 2016-07-27 A kind of footwear low temperature resistant EVA adhesives and preparation method thereof Active CN106189961B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106863965A (en) * 2017-02-27 2017-06-20 合肥中科富华新材料有限公司 A kind of self-priming water, shock film and preparation method
CN109207072A (en) * 2018-08-15 2019-01-15 广东尚联新材料科技有限公司 It is a kind of applied between wooden boards or wooden boards and PVC board bonding EVA adhesive film and preparation method
CN109280530A (en) * 2018-09-11 2019-01-29 平湖展鹏热熔胶膜有限公司 Hot melt adhesive functional material and preparation method thereof, hot melt adhesive are cast naked membrane preparation method
CN109735118A (en) * 2019-01-05 2019-05-10 青岛马基泰商贸有限公司 A kind of environment protection colour sealing wax and preparation method thereof, application
CN113969054A (en) * 2021-11-30 2022-01-25 广东国立科技股份有限公司 EVA modified polyurethane composite shoe material and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101787250A (en) * 2010-01-22 2010-07-28 山东久隆高分子材料有限公司 EVA hot melt adhesive composition containing linear hydroxyl-terminated polyurethane resin
CN103756576A (en) * 2013-12-12 2014-04-30 江阴伟韬塑料新材料有限公司 Hot melt adhesive film for adhering sole, and preparation method thereof
CN103756577A (en) * 2013-12-31 2014-04-30 广州鹿山新材料股份有限公司 PVC (polyvinyl chloride)/metal bonding hot melt adhesive film and preparation method thereof
CN105238303A (en) * 2015-11-02 2016-01-13 华东理工大学 Polyethylene-vinyl acetate hot-melt adhesive and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101787250A (en) * 2010-01-22 2010-07-28 山东久隆高分子材料有限公司 EVA hot melt adhesive composition containing linear hydroxyl-terminated polyurethane resin
CN103756576A (en) * 2013-12-12 2014-04-30 江阴伟韬塑料新材料有限公司 Hot melt adhesive film for adhering sole, and preparation method thereof
CN103756577A (en) * 2013-12-31 2014-04-30 广州鹿山新材料股份有限公司 PVC (polyvinyl chloride)/metal bonding hot melt adhesive film and preparation method thereof
CN105238303A (en) * 2015-11-02 2016-01-13 华东理工大学 Polyethylene-vinyl acetate hot-melt adhesive and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106863965A (en) * 2017-02-27 2017-06-20 合肥中科富华新材料有限公司 A kind of self-priming water, shock film and preparation method
CN109207072A (en) * 2018-08-15 2019-01-15 广东尚联新材料科技有限公司 It is a kind of applied between wooden boards or wooden boards and PVC board bonding EVA adhesive film and preparation method
CN109280530A (en) * 2018-09-11 2019-01-29 平湖展鹏热熔胶膜有限公司 Hot melt adhesive functional material and preparation method thereof, hot melt adhesive are cast naked membrane preparation method
CN109735118A (en) * 2019-01-05 2019-05-10 青岛马基泰商贸有限公司 A kind of environment protection colour sealing wax and preparation method thereof, application
CN109735118B (en) * 2019-01-05 2023-10-24 青岛马基泰商贸有限公司 Environment-friendly color sealing wax and preparation method and application thereof
CN113969054A (en) * 2021-11-30 2022-01-25 广东国立科技股份有限公司 EVA modified polyurethane composite shoe material and preparation method thereof

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